CN107849747B - Spandex fiber with good chlorine resistance - Google Patents
Spandex fiber with good chlorine resistance Download PDFInfo
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- CN107849747B CN107849747B CN201680040533.XA CN201680040533A CN107849747B CN 107849747 B CN107849747 B CN 107849747B CN 201680040533 A CN201680040533 A CN 201680040533A CN 107849747 B CN107849747 B CN 107849747B
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- Prior art keywords
- compound
- chlorine resistance
- spandex fiber
- hydrotalcite
- chlorine
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000460 chlorine Substances 0.000 title claims abstract description 60
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 60
- 229920002334 Spandex Polymers 0.000 title claims abstract description 49
- 239000004759 spandex Substances 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title claims abstract description 46
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 33
- 229960001545 hydrotalcite Drugs 0.000 claims description 33
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 30
- -1 diaminourea compound Chemical class 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 18
- 229920003226 polyurethane urea Polymers 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 238000000578 dry spinning Methods 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910020038 Mg6Al2 Inorganic materials 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 229910000515 huntite Inorganic materials 0.000 claims description 5
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 3
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- WVFDILODTFJAPA-UHFFFAOYSA-M sodium;1,4-dihexoxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCC WVFDILODTFJAPA-UHFFFAOYSA-M 0.000 claims description 3
- ZRHAQPGGMXXARO-UHFFFAOYSA-N 1,1-diamino-3,3-dimethylurea Chemical compound CN(C(=O)N(N)N)C ZRHAQPGGMXXARO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 claims description 2
- UMEWSJNRBXKWKZ-UHFFFAOYSA-M sodium;1,4-dioxo-1,4-dipentoxybutane-2-sulfonate Chemical compound [Na+].CCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCC UMEWSJNRBXKWKZ-UHFFFAOYSA-M 0.000 claims description 2
- FXZAUBIBKADOBA-UHFFFAOYSA-N 1,4-bis(2-methylpropoxy)-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CC(C)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(C)C FXZAUBIBKADOBA-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to spandex fibers having improved strength and good chlorine resistance comprising a dialkyl sulfosuccinate of formula (1), wherein R is1And R2Are identical or different and are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and M+Is H+、Li+、Na+、K+Or NH4 +A cation-like species.
Description
Technical Field
The present invention relates to a spandex fiber having good chlorine resistance, and more particularly, to a spandex fiber having improved strength and good chlorine resistance, which comprises a dialkyl sulfosuccinate represented by chemical formula (1).
[ chemical formula 1]
Wherein R is1And R2Are identical or different and are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and M+Is H+、Li+、Na+、K+Or NH4 +A cation-like species.
Background
Spandex fiber is widely used for underwear, socks, sportswear, and the like, because it maintains high rubber elasticity and is excellent in physical properties such as tensile stress, restorability, and the like.
However, when washing is performed by chlorine bleaching, the physical properties of the polyurethane part, which is the main component of spandex fibers, are significantly reduced, and even in the case of swimwear manufactured by interweaving spandex fibers and polyamide fibers, the physical properties of spandex fibers are reduced after contact with chlorine water (active chlorine concentration 0.5 to 3.5ppm) in a swimming pool.
In this regard, in order to improve chlorine resistance of spandex fibers, efforts are continuously made to improve chlorine resistance of spandex fibers, as chlorine resistance agents used in spandex fibers, U.S. patent publication No. 4,340,527 discloses zinc oxide, U.S. patent publication No. 5,626,960 discloses a mixture of huntite and hydromagnesite, korean patent publication No. 92-3250 discloses calcium carbonate and barium carbonate, japanese patent publication No. 6-81215 discloses a MgO/ZnO solid solution (solid solution), japanese patent publication No. 59-133248 discloses magnesium oxide, magnesium hydroxide or hydrotalcite, and japanese patent publication No. 3-292364 discloses hydrotalcite treated with a higher fatty acid and a silane coupling agent.
In addition, in U.S. patent publication No. 5,447,969, hydrotalcite having crystalline water and C10-C30 fatty acids attached thereto is used, by improving the dispersibility of hydrotalcite, thereby preventing the coagulation of hydrotalcite during the production of spandex fibers, and improving the discharge pressure (discharge pressure) increase and yarn breakage (yarn breakage) phenomenon during spinning, without causing browning of spandex fibers even if treated with a tannin solution, and without causing swelling of the fibers even when soaked in chlorine water.
In U.S. patent publication No. 6,692,828, hydrotalcite coated with melamine-based compounds, which is excellent in heat resistance, is used as a chlorine-resistant agent for spandex fibers, but the degree thereof is not as high as in U.S. patent publication No. 5,447,969, and even when the hydrotalcite is used, discoloration of the spandex fibers is caused when dry spinning is performed in hot air at 250 ℃.
In european patent publication No. 1262499 a1, attempts have been made to improve the chlorine resistance of spandex fibers by grinding (milling) hydrotalcite to an average particle size of 1 μm or less and using it as a chlorine resistance agent.
Specifically, unlike the prior art, with respect to the structural formula of hydrotalcite disclosed in european patent publication No. 1262499 a1, it can be seen that part of carbonate ions are decomposed into carbon dioxide and oxygen, thus showing a hydrotalcite structure having residual oxygen and being partially decarbonated. The content of carbonate ions in the hydrotalcite plays an important role in imparting chlorine resistance to spandex fibers, and thus adding hydrotalcite having a low content of carbonate ions to spandex polymers results in a decrease in the chlorine resistance of spandex.
In korean patent publication No. 2006-5814, spandex fibers having good discoloration resistance and chlorine resistance were manufactured by using hydrotalcite coated with a melamine-based compound and from which crystalline water was removed, and such hydrotalcite from which only crystalline water was removed without undergoing dehydroxylation or decarbonation was easily changed back to hydrotalcite having an initial state of crystalline water due to its high hygroscopicity, and thus considerable attention was required for the treatment.
Further, even if crystal water of hydrotalcite is removed, hydrotalcite absorbs moisture in the dope or polymer during spandex manufacturing, manufacturing the dope, or mixing the dope and the polymer to become hydrotalcite having crystal water, and thus discoloration of the filaments is caused when the spandex polymer disclosed in the patent is spun at a temperature of 250 ℃ or more.
In korean patent publication No. 2006-.
Thus, the conventional patents relating to chlorine-resistant spandex fibers basically employ inorganic chlorine-resistant agents, and the effects thereof are confirmed by using organic additives in order to improve the durability of chlorine resistance. However, such chlorine-resistant spandex fibers generally have reduced strength after treatment with chlorinated water.
Disclosure of Invention
Technical problem
The present inventors have found that when the fiber strength is improved, the high strength is maintained even after the treatment with chlorine water, and therefore, the chlorine resistance improving effect is brought about, thereby completing the present invention, and the object of the present invention is to improve the chlorine resistance by adding an additive capable of improving the strength.
Means for solving the problems
The present invention is characterized in that a spandex fiber having improved strength and good chlorine resistance is manufactured by dry spinning using a polyurethaneurea spinning dope comprising a polyurethaneurea polymer, an inorganic chlorine-resistant agent, an additive selected from the group of mono-hindered hydroxyphenyl-containing compounds, an additive containing a diaminourea-based compound, and 0.01 to 10 wt% of a dialkyl sulfosuccinate represented by the following chemical formula 1:
[ chemical formula 1]
Wherein R is1And R2Are identical or different and are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and M+Is H+、Li+、Na+、K+Or NH4 +A cation-like species.
Effects of the invention
The present invention provides an effect of improving chlorine resistance by improving strength by adding an additive having a strength-improving function to a conventional chlorine-resistant fiber.
Also, the additive improves adhesion between filaments (필라멘트), thus preventing a phenomenon of filament breakage (사걸) or formation of a band on a fabric due to a decrease in filament bundling property due to friction in a knitting machine using spandex fiber, thereby improving processability.
Detailed Description
The present invention is described in detail below, and the following examples are for illustrative purposes only and are not intended to limit the present invention.
The term "spandex fiber" used in the present invention means a rayon fiber which is a long-chain synthetic elastomer having a fiber-forming substance of 85 wt% or more. That is, a fiber is formed by melt spinning or dry spinning as described above after polyurethane is produced from a mixture of a polyether polyol and a diisocyanate and a chain extender.
As known in the art, the polyurethane prepolymer solution for manufacturing spandex fiber of the present invention can be prepared by reacting an organic diisocyanate and a polymer diol to form a polyurethane prepolymer, followed by dissolution with an organic solvent (e.g., dimethylacetamide), followed by reaction with a diamine and a monoamine.
The organic diisocyanate used in the present invention may be 4,4 '-diphenylmethane-4, 4' -diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated p, p-methylene diisocyanate, etc., and polytetramethylene ether glycol, polypropylene glycol, polycarbonate glycol, etc., may be used as the polymer glycol.
Examples of the above-mentioned diamine used as a chain extender include ethylenediamine, propylenediamine, hydrazine, 1, 2-diaminopropane and the like. In particular, in the present invention, ethylenediamine and 1, 2-diaminopropane mixed in a ratio of 80 mol% and 20 mol% may be used. In addition, a monoamine is used as the chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine and the like.
In the present invention, in order to prevent discoloration and deterioration of physical properties of spandex due to ultraviolet rays, atmospheric fumes, heat treatment during spandex processing, and the like, a polyurethaneurea spinning dope is produced by adding a light resistance agent, an antioxidant, an inorganic chlorine resistance agent, a strength-improving additive, and the like.
Then, dry spinning is performed using the polyurethane urea spinning dope obtained above, thereby forming a spandex fiber.
According to one embodiment of the invention, the light-fastness agent comprises titanium dioxide or magnesium stearate, added in an amount of 0.1% to 1.0% by weight, preferably 0.3% to 0.6% by weight, with respect to the solid content of the polyurethaneurea polymer.
Examples of the antioxidant include urethane-based additives having an antioxidant effect, containing a t-butyl group, which can be added and mixed at about 0.1 wt% to 1.0 wt%, and the urethane-based additives may be compounds prepared by copolymerizing t-butyl diethanolamine and 4,4' -methylenebis (cyclohexyl isocyanate).
As the inorganic chlorine resisting agent, a hydrotalcite compound, a mixed mineral of huntite and hydromagnesite, or a hydromagnesite compound may be used.
Hydrotalcite compounds, e.g. Mg4Al2(OH)12CO3·3H2O、Mg4.5Al2(OH)13CO3·3.5H2O、Mg6Al2(OH)16CO3·H2O、Mg8Al2(OH)20CO3·H2O、Mg4Al2(OH)12CO3·H2O、Mg4.5Al2(OH)13CO3、Mg6Al2(OH)16CO3、Mg8Al2(OH)20CO3、Mg4Al2(OH)20CO3、Mg4.5Al2(OH)13(CO3)0.6O0.4、Mg6Al2(OH)16(CO3)0.7O0.3、Mg4.5Al2(OH)12.2(CO3)0.8O0.6、Mg4Al2(OH)12(CO3)0.6O0.4Etc., wherein Mg is preferably used4Al2(OH)12CO3·3H2O。
The hydrotalcite has a characteristic of absorbing moisture, and thus when it is not subjected to a coating treatment, gelation and coagulation occur when it is added to a polyurethane polymer, which may cause filament breakage during spinning. The hydrotalcite may be subjected to a coating treatment in order to block the hydrotalcite from absorbing water and improve its dispersibility, and to improve the discharge pressure increase and filament breakage during spinning. Even in the case of using the hydrotalcite which is not coated, when sand grinding or milling is performed, spinnability is the same as that of using the hydrotalcite coated.
According to the invention, 1% to 10% by weight of hydrotalcite compound relative to the polymer of the polyurethane solution is added and mixed; the hydrotalcite is coated with 1 to 3 wt% of stearic acid and 0.5 to 2 wt% of a melamine based compound, relative to the hydrotalcite compound. The melamine compound is preferably melamine polyphosphate (melaminephosphosulfate).
When the contents of the stearic acid and the melamine-based compound are less than 1 wt% or 0.5 wt%, respectively, the coating effect cannot be exerted, and conversely, when they exceed 3 wt% or 10 wt%, respectively, there is not much difference in the coating effect, but it is disadvantageous in economical aspects.
The chemical formula of the huntite compound is Mg3Ca(CO3)4Exemplary compounds of hydromagnesite include Mg5(CO3)4(OH)2·4H2O、Mg4(CO3)4·Mg(OH)2·H2O、Mg3(CO3)3·Mg(OH)2·3H2O、Mg4(CO3)4·Mg(OH)2And Mg3(CO3)3·Mg(OH)2、MgCO3And the like. The mixing ratio of huntite and hydromagnesite by weight is 90:10, 80:20, 70:30, 60:40 or 40:60 etc., preferably the ratio is 60: 40.
In addition, in order to improve chlorine resistance, as an additive, a mono-hindered hydroxyphenyl group-containing compound such as 1,1, 3-tris (2' -methyl-4 ' -hydroxy-5 ' -t-butylphenyl) butane may be used, and the content thereof is preferably 0.1 to 3.0 wt% with respect to the solid content of the polyurethaneurea polymer.
As the additive containing the diaminourea-based compound having heat resistance and a radical scavenger function, 0.1 wt% to 3.0 wt% of a hindered amine compound 1,1,1',1' -tetramethyl-4, 4' - (methylene-di-p-phenylene) diaminourea or 1, 6-hexamethylene bis (N, N-dimethyldiaminourea) may be used, and preferably 0.3 wt% to 1.2 wt% may be added and mixed.
As the strength-improving additive, it is preferable to use 0.01 to 10% by weight of the dialkyl sulfosuccinate of the formula (1).
[ chemical formula 1]
Wherein R is1And R2Are identical or different and are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and M+Is H+、Li+、Na+、K+Or NH4 +A cation-like species.
Examples of the dialkyl sulfosuccinate represented by the above chemical formula (1) include: diisobutyl ester sodium sulfosuccinate, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, dipentyl sodium sulfosuccinate, dicyclohexyl sodium sulfosuccinate. Preferably, the dialkyl sulfosuccinates are dioctyl sodium sulfosuccinate and dihexyl sodium sulfosuccinate.
According to the present invention, in order to use a dialkyl sulfosuccinate, a process of dissolution in a solvent is required, and mixing with a slurry after dissolution can improve dispersibility, thereby improving strand uniformity. When the slurry is mixed, it is preferable to prepare a 35 to 55% solution by dissolving with a dimethylacetamide solvent in order to improve dispersibility.
As described above, an inorganic chlorine-resistant agent, an additive for improving the function thereof, an organic additive, and the like are added to and mixed with a polyurethane solution, and the obtained spinning dope is defoamed, and then spun and wound by a dry spinning process to produce a spandex fiber having improved strength and excellent chlorine resistance.
The spandex fiber having improved strength and excellent chlorine resistance according to the present invention is characterized in that the chlorine resistance is greatly improved by using a dialkyl sulfosuccinate, unlike a conventional spandex fiber manufacturing method in which the chlorine resistance is improved by using an inorganic additive and an organic additive. Chlorine resistance is evaluated by the retention rate of spandex filament strength before and after chlorine water treatment, and the higher the strength maintenance of spandex filaments, the more excellent the chlorine resistance. The use of the dialkyl sulfosuccinate not only improves the strength of the strands but also extends the duration of the strength retention after the chlorine water treatment, so that the chlorine resistance improving effect is superior to that of the prior art.
Hereinafter, the present invention will be described in detail by way of examples and comparative examples.
Examples
Example 1
518g of diphenylmethane-4, 4' -diisocyanate and 2328g of polytetramethylene ether glycol (molecular weight 1800) were stirred and reacted at 90 ℃ for 95 minutes in a nitrogen stream to produce a polyurethane prepolymer having isocyanates at both ends. After the prepolymer was cooled to room temperature, 4269g of dimethylacetamide was added and dissolved, thereby obtaining a polyurethane prepolymer solution.
Subsequently, 43g of ethylenediamine and 9.1g of diethylamine were dissolved in 1889g of dimethylacetamide and added to the above prepolymer solution at 9 ℃ or lower, thereby obtaining a polyurethane solution. The following were added as additives and mixed with respect to the solid content of the above polymer: 0.5 wt% titanium dioxide as a light stabilizer; 4 wt% hydrotalcite Mg as chlorine resistant agent4Al2(OH)12CO3·3H2O, the hydrotalcite is coated with 2.0 wt% stearic acid, 1 wt% melamine polyphosphate, relative to the hydrotalcite. The following were added to the slurry and mixed: 0.8 wt% of mono-hindered hydroxyphenyl compound 1,1, 3-tris (2 '-methyl-4' -hydroxy-5 '-t-butylphenyl) butane, 0.5 wt% of diaminourea compound 1,1,1',1 '-tetramethyl-4, 4' - (methylene-di-p-phenylene) diaminourea and 0.5 wt% of dialkyl sulfosuccinate, to obtain a polyurethaneurea spinning dope.
After defoaming the dope, the dope was wound at a spinning temperature of 260 ℃ and a winding speed of 900m/min in a dry spinning process to produce a spandex fiber of 3filaments and 40 deniers (3filaments and 40denier), and the physical properties and chlorine resistance thereof were evaluated, and the evaluation results are shown in table 1. In order to evaluate the chlorine resistance of the obtained spandex filament, the strength retention in chlorine water was evaluated as follows.
[ degree of Strength extension ]
A specimen having a length of 10cm was measured at a drawing speed of 100cm/min by means of a MEL machine. At this time, values of the elongation and strength at the time of yarn breakage were measured, and the load (200% modulus) of the yarn at the time of 200% stretching of the yarn was measured.
[ evaluation of chlorine resistance ]
When spandex fiber is stretched by 50%, the spandex fiber is treated in water at 99-100 ℃ for 1 hour, dried and cooled at normal temperature, and immersed in chlorine water having an active chlorine content of 3.5ppm and a pH of 7.6 at normal temperature for 120 hours, and then the strength retention rate is calculated by the following formula. The MEL machine was used to evaluate the strength, the specimen length was 10cm, and the measurement was carried out using a load cell (cell) of 32kgf at a tensile speed of 1000mm/min (crosshead speed ).
Strength retention (%) ═ S/So×100
(So: strength before treatment; s: strength after treatment)
Example 2
After a dope was prepared in the same manner as in example 1 except that 1.0 wt% of dialkyl sulfosuccinate was added and mixed, dry spinning was performed at a speed of 900m/min to manufacture polyurethane urea elastic yarn of 40denier3filaments (40denier3filaments), which was evaluated for physical properties, and the evaluation results were as shown in table 1.
Example 3
After a dope was prepared in the same manner as in example 1 except that 2.0 wt% of dialkyl sulfosuccinate was added and mixed, dry spinning was performed at a speed of 900m/min to manufacture polyurethane urea elastic yarn of 40denier3filaments (40denier3filaments), which was evaluated for physical properties, and the evaluation results were as shown in table 1.
Comparative example 1
A spinning dope was prepared in the same manner as in example 1 except that the dialkyl sulfosuccinate was not added, and then dry-spun at a speed of 900m/min to produce a 40denier3filament (40denier3filaments) polyurethaneurea elastic yarn, which was evaluated for physical properties, and the evaluation results were as shown in table 1.
Table 1: evaluation results of physical Properties and chlorine resistance of the yarn
Claims (6)
1. A spandex fiber having improved strength and good chlorine resistance, wherein the spandex fiber is prepared by dry-spinning a polyurethaneurea spinning dope for preparing a spandex fiber having good chlorine resistance by spinning, the polyurethaneurea spinning dope comprising an inorganic chlorine-resistant agent added to a conventional polyurethaneurea polymer, an additive for improving chlorine resistance, an additive containing a diaminourea compound having heat resistance and a radical scavenger function, and a dialkylsulfosuccinate represented by chemical formula 1,
wherein the polyurethaneurea spinning dope comprises 0.1 wt% to 3.0 wt% of a mono-hindered hydroxyphenyl group-containing compound as an additive for improving chlorine resistance and 0.01 wt% to 10 wt% of a dialkyl sulfosuccinate represented by chemical formula 1, relative to a polyurethaneurea polymer;
[ chemical formula 1]
Wherein R is1And R2Are identical or different and are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and M+Is H+、Li+、Na+、K+Or NH4 +A cation-like species.
2. The spandex fiber with improved strength and good chlorine resistance according to claim 1, wherein the inorganic chlorine-resistance agent is selected from hydrotalcite compounds, huntite [ Mg [ ]3Ca(CO3)4]A mixed mineral with hydromagnesite or a hydromagnesite compound; wherein the hydrotalcite compound is Mg4Al2(OH)12CO3·3H2O、Mg4.5Al2(OH)13CO3·3.5H2O、Mg6Al2(OH)16CO3·H2O、Mg8Al2(OH)20CO3·H2O、Mg4Al2(OH)12CO3·H2O、Mg4.5Al2(OH)13CO3、Mg6Al2(OH)16CO3、Mg8Al2(OH)20CO3、Mg4Al2(OH)20CO3、Mg4.5Al2(OH)13(CO3)0.6O0.4、Mg6Al2(OH)16(CO3)0.7O0.3、Mg4.5Al2(OH)12.2(CO3)0.8O0.6Or Mg4Al2(OH)12(CO3)0.6O0.4(ii) a The hydromagnesite compound is Mg4(CO3)4·Mg(OH)2·H2O、Mg3(CO3)3·Mg(OH)2·3H2O、Mg4(CO3)4·Mg(OH)2Or Mg3(CO3)3·Mg(OH)2、MgCO3。
3. The spandex fiber with improved strength and good chlorine resistance according to claim 2, wherein 1 to 10 wt% of the hydrotalcite compound is added and mixed relative to the polyurethaneurea polymer; the hydrotalcite is coated with 1-3 wt% of stearic acid, 0.5-2 wt% of melamine-based compound, relative to the hydrotalcite compound.
4. The spandex fiber with improved strength and good chlorine resistance according to claim 1, wherein the mono-hindered hydroxyphenyl-containing compound is 1,1, 3-tris (2' -methyl-4 ' -hydroxy-5 ' -tert-butylphenyl) butane.
5. The spandex fiber with improved strength and good chlorine resistance according to claim 1, wherein the diaminourea compound-containing additive is a hindered amine compound 1,1,1',1' -tetramethyl-4, 4' - (methylene-di-p-phenylene) diamino urea or 1, 6-hexamethylene bis (N, N-dimethyldiamino urea) added in an amount of 0.1 to 3.0 wt%.
6. The spandex fiber with improved strength and good chlorine resistance according to claim 1, wherein the dialkyl sulfosuccinate of formula (1) is one selected from the group consisting of diisobutyl sulfosuccinate sodium, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, dipentyl sodium sulfosuccinate and dicyclohexyl sodium sulfosuccinate.
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| PCT/KR2016/006425 WO2017010692A1 (en) | 2015-07-10 | 2016-06-16 | Spandex fiber with excellent chlorine resistance |
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| CN1513026A (en) * | 2001-06-05 | 2004-07-14 | �Ű˾ | Spandex containing mixture of phenolic compounds |
| WO2012091468A2 (en) * | 2010-12-30 | 2012-07-05 | 주식회사 효성 | Spandex fiber having improved chlorine resistance and discoloration resistance, and method for preparing same |
| CN102666947A (en) * | 2009-09-30 | 2012-09-12 | 株式会社晓星 | Spandex fiber with excellent chlorine resistance, and preparation method thereof |
| CN103339303A (en) * | 2010-12-29 | 2013-10-02 | 晓星株式会社 | Polyurethane fiber having superior adhesive force between filaments in multi-filament elastic fiber and method for manufacturing same |
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| KR0131832B1 (en) * | 1995-07-11 | 1998-04-16 | 박홍기 | Manufacturing method of polyurethan elastic fiber |
| KR101238495B1 (en) * | 2010-12-30 | 2013-03-04 | 주식회사 효성 | Discoloration-resistant and chlorine-resistant Spandex Fiber and Preparation Method thereof |
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| CN1226577A (en) * | 1998-02-09 | 1999-08-25 | 拜尔公司 | Polyurethanes and elastane fibres finished to render them antistatic |
| CN1513026A (en) * | 2001-06-05 | 2004-07-14 | �Ű˾ | Spandex containing mixture of phenolic compounds |
| CN102666947A (en) * | 2009-09-30 | 2012-09-12 | 株式会社晓星 | Spandex fiber with excellent chlorine resistance, and preparation method thereof |
| CN103339303A (en) * | 2010-12-29 | 2013-10-02 | 晓星株式会社 | Polyurethane fiber having superior adhesive force between filaments in multi-filament elastic fiber and method for manufacturing same |
| WO2012091468A2 (en) * | 2010-12-30 | 2012-07-05 | 주식회사 효성 | Spandex fiber having improved chlorine resistance and discoloration resistance, and method for preparing same |
| KR20140054509A (en) * | 2012-10-29 | 2014-05-09 | 주식회사 효성 | Improved chlrorine and discolored resistant spandex fiber and method for preparing the same |
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